Melt Processing and Properties of Polyamide 6/Graphene Nanoplatelet Composites

Graphene, due to its outstanding properties, has become the topic of much research activity in recent years. Much of that work has been on a laboratory scale however, if we are to introduce graphene into real product applications it is necessary to examine how the material behaves under industrial processing conditions. In this paper the melt processing of polyamide 6/graphene nanoplatelet composites via twin screw extrusion is investigated and structure–property relationships are examined for mechanical and electrical properties. Graphene nanoplatelets (GNPs) with two aspect ratios (700 and 1000) were used in order to examine the influence of particle dimensions on composite properties. It was found that the introduction of GNPs had a nucleating effect on polyamide 6 (PA6) crystallization and substantially increased crystallinity by up to 120% for a 20% loading in PA6. A small increase in crystallinity was observed when extruder screw speed increased from 50 rpm to 200 rpm which could be attributed to better dispersion and more nucleation sites for crystallization. A maximum enhancement of 412% in Young's modulus was achieved at 20 wt% loading of GNPs. This is the highest reported enhancement in modulus achieved to date for a melt mixed thermoplastic/GNPs composite. A further result of importance here is that the modulus continued to increase as the loading of GNPs increased even at 20 wt% loading and results are in excellent agreement with theoretical predictions for modulus enhancement. Electrical percolation was achieved between 10–15 wt% loading for both aspect ratios of GNPs with an increase in conductivity of approximately 6 orders of magnitude compared to the unfilled PA6.

Structural and electrical anisotropy of (001)-, (116)-, and (103)-oriented epitaxial SrBi2Ta2O9 thin films on SrTiO3 substrates grown by pulsed laser deposition

Epitaxial SrBi2Ta2O9 (SBT) thin films with well-defined (001), (116), and (103) orientations have been grown by pulsed laser deposition on (001)-, (011)-, and (111)-oriented Nb-doped SrTiO3 substrates. X-ray diffraction pole figure and phi -scan measurements revealed that the three-dimensional epitaxial orientation relation SBT(001)parallel to SrTiO3(001), and SBT[1(1) over bar 0]parallel to SrTiO3[100] is valid for all cases of SET thin films on SrTiO3 substrates, irrespective of their orientations. Atomic force microscopy images of the c-axis-oriented SET revealed polyhedron-shaped grains showing spiral growth around screw dislocations. The terrace steps of the c-axis-oriented SET films were integral multiples of a quarter of the lattice parameter c of SBT (similar to 0.6 nm). The grains of (103)-oriented SET films were arranged in a triple-domain configuration consistent with the symmetry of the SrTiO3(111) substrate. The measured remanent polarization (2P(r)) and coercive field (2E(c)) of (116)-oriented SBT films were 9.6 muC/cm(2) and 168 kV/cm, respectively, for a maximum applied electric field of 320 kV/cm. Higher remanent polarization (2P(r)=10.4 muC/cm(2)) and lower coercive field (2E(c)=104 kV/cm) than those of SBT(116) films were observed in (103)-oriented SET thin films, and (001)-oriented SET revealed no ferroelectricity along the [001] axis. The dielectric constants of (001)-, (116)-, and (103)-oriented SBT were 133, 155, and 189, respectively. (C) 2000 American Institute of Physics.

Viscosity Control for Extrusion Processes Using Recycled Polymers

The aim of this paper is to develop a new extruder control system for recycled materials which has ability to automatically maintain constant a polymer melt viscosity of mixed recycled polymers during extrusion, regardless of variations in the Melt Flow Index (MFI) of recycled mixed grade high density polyethylene (HDPE) feedstock. A closed-loop controller is developed to automatically regulate screw speed and barrel temperature profile to achieve constant viscosity and enable consistent processing of variable grade recycled HDPE materials. The experimental results of real time viscosity measurement and control using a 38mm single screw extruder with different recycled HDPEs with widely different MFIs are reported in this work

Melt Processing and Properties of Polyamide 6/Graphene Nanoplatelet Composites

In this paper, the processing and characterization of Polyamide 6 (PA6) / graphite nanoplatelets
(GNPs) composites is reported. PA6/GNPs composites were prepared by melt-mixing using an
industrial, co-rotating, intermeshing, twin-screw extruder. A bespoke screw configuration was used
that was designed in-house to enhance nanoparticle dispersion into a polymer matrix. The effects of
GNPs type (xGnP® M-5 and xGnP® C-500), GNPs content, and extruder screw speed on the bulk
properties of the PA6/GNPs nanocomposites were investigated. Results show a considerable
improvement in the thermal and mechanical properties of PA6/GNPs composites, as compared with
the unfilled PA6 polymer. An increase in crystallinity (%Xc) with increasing GNPs content, and a
change in shape of the crystallization exotherms (broadening) and melting endotherms, both suggest a
change in the crystal type and perfection. An increase in tensile modulus of as much as 376% and
412% was observed for PA6/M-5 xGnP® and PA6/C-500 xGnP® composites, respectively, at filler
contents of 20wt%. The enhancement of Young’s modulus and yield stress can be attributed to the
reinforcing effect of GNPs and their uniform dispersion in the PA6 matrix. The rheological response
of the composite resembles that of a ‘pseudo-solid’, rather than a molten liquid, and analysis of the
rheological data indicates that a percolation threshold was reached at GNPs contents of between 10–
15wt%. The electrical conductivity of the composite also increased with increasing GNPs content,
with an addition of 15wt% GNPs resulting in a 6 order-of-magnitude increase in conductivity. The
electrical percolation thresholds of all composites were between 10–15wt%.

Characterisation of melt processed nanocomposites of Polyamide 6 subjected to uniaxial-drawing

In this paper, the processing and characterization of Polyamide 6 (PA6) nanocomposites containing graphite nanoplatelets (GNPs) is reported. PA6 nanocomposites were prepared by melt-mixing using an industrial, co-rotating, intermeshing, twin-screw extruder. A bespoke screw configuration was used that was designed in-house to enhance nanoparticle dispersion into a polymer matrix. The effects of nano-filler type (xGnPTM M-5 and xGnPTM C-500), nano-filler content, and extruder screw speed on the bulk properties of the PA6 nanocomposites were investigated. The crystalline structures of PA6 nanocomposites are related to thermal treatment, stress history and the presence of moisture and nanofillers. DSC, Raman and XRD studies show an increase in crystallinity with increasing GNP content and a phase transformation between α-form to γ-form crystals as a result of the heterophase nucleation effect. The effect of uniaxial stretching on PA6 nanocomposites was investigated by drawing specimens heated at temperatures below the melting temperature. DSC and Raman studies on the drawn samples show an increase in yield stress as the GNP content increases due to the strain induced crystallization and γ—β transition during stretching. The rheological response of the nanocomposites resemble that of a ‘pseudo-solid’, rather than a molten liquid, and analysis of the rheological data indicates that a percolation threshold was reached at GNP contents of between 10–15wt%. An increase in tensile modulus of as much as 412% was observed for PA6/C-500 xGnPTM composites, at a filler content of 20wt%. The enhancement of Young’s modulus and yield stress can be attributed to the reinforcing effect of GNPs and their uniform dispersion in the PA6 matrix. The electrical conductivity of the composite also increased with increasing GNP content, with an addition of 15wt% GNP resulting in a 6 order-of-magnitude increase in conductivity. The effects of uniaxial-drawing and the inclusion of multiple nano-filler varieties on the electrical and mechanical properties are currently under investigation.

Characterization and structure–property relationship of melt-mixed high density polyethylene/multi-walled carbon nanotube composites under extensional deformation

Melt-mixed high density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites with 1–10 wt% MWCNTs were prepared by twin screw extrusion and compression moulded into sheet form. The compression moulded nanocomposites exhibit a 112% increase in modulus at a MWCNT loading of 4 wt%, and a low electrical percolation threshold of 1.9 wt%. Subsequently, uniaxial, sequential (seq-) biaxial and simultaneous (sim-) biaxial stretching of the virgin HDPE and nanocomposite sheets was conducted at different strain rates and stretching temperatures to investigate the processability of HDPE with the addition of nanotubes and the influence of deformation on the structure and final properties of nanocomposites. The results show that the processability of HDPE is improved under all the uniaxial and biaxial deformation conditions due to a strengthened strain hardening behaviour with the addition of MWCNTs. Extensional deformation is observed to disentangle nanotube agglomerates and the disentanglement degree is shown to depend on the stretching mode, strain rate and stretching temperatures applied. The disentanglement effectiveness is: uniaxial stretching < sim-biaxial stretching < seq-biaxial stretching, under the same deformation parameters. In sim-biaxial stretching, reducing the strain rate and stretching temperature can lead to more nanotube agglomerate breakup. Enhanced nanotube agglomerate disentanglement exhibits a positive effect on the mechanical properties and a negative effect on the electrical properties of the deformed nanocomposites. The ultimate stress of the composite containing 4 wt% MWCNTs increased by ∼492% after seq-biaxial stretching, while the resistivity increased by ∼1012 Ω cm.

Investigation of the temperature homogeneity of die melt flows in polymer extrusion

Polymer extrusion is fundamental to the processing of polymeric materials and melt flow temperature homogeneity is a major factor which influences product quality. Undesirable thermal conditions can cause problems such as melt degradation, dimensional instability, weaknesses in mechanical/optical/geometrical properties, and so forth. It has been revealed that melt temperature varies with time and with radial position across the die. However, the majority of polymer processes use only single-point techniques whose thermal measurements are limited to the single point at which they are fixed. Therefore, it is impossible for such techniques to determine thermal homogeneity across the melt flow. In this work, an extensive investigation was carried out into melt flow thermal behavior of the output of a single extruder with different polymers and screw geometries over a wide range of processing conditions. Melt temperature profiles of the process output were observed using a thermocouple mesh placed in the flow and results confirmed that the melt flow thermal behavior is different at different radial positions. The uniformity of temperature across the melt flow deteriorated considerably with increase in screw rotational speed while it was also shown to be dependent on process settings, screw geometry, and material properties. Moreover, it appears that the effects of the material, machine, and process settings on the quantity and quality of the process output are heavily coupled with each other and this may cause the process to be difficult to predict and variable in nature

Effect of cooling rate on the properties of high density polyethylene/multi-walled carbon nanotube composites

High density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by melt mixing using twin-screw extrusion. The extruded pellets were compression moulded at 200°C for 5min followed by cooling at different cooling rates (20°C/min and 300°C/min respectively) to produce sheets for characterization. Scanning electron microscopy (SEM) shows that the MWCNTs are uniformly dispersed in the HDPE. At 4 wt% addition of MWCNTs composite modulus increased by over 110% compared with the unfilled HDPE (regardless of the cooling rate). The yield strength of both unfilled and filled HDPE decreased after rapid cooling by about 10% due to a lower crystallinity and imperfect crystallites. The electrical percolation threshold of composites, irrespective of the cooling rate, is between a MWCNT concentration of 1∼2 wt%. Interestingly, the electrical resistivity of the rapidly cooled composite with 2 wt% MWCNTs is lower than that of the slowly cooled composites with the same MWCNT loading. This may be due to the lower crystallinity and smaller crystallites facilitating the formation of conductive pathways. This result may have significant implications for both process control and the tailoring of electrical conductivity in the manufacture of conductive HDPE/MWCNT nanocomposites.

Optimising drug solubilisation in amorphous polymer dispersions: rational selection of hot-melt extrusion processing parameters

The aim of this article was to construct a T–ϕ phase diagram for a model drug (FD) and amorphous polymer (Eudragit® EPO) and to use this information to understand the impact of how temperature–composition coordinates influenced the final properties of the extrudate. Defining process boundaries and understanding drug solubility in polymeric carriers is of utmost importance and will help in the successful manufacture of new delivery platforms for BCS class II drugs. Physically mixed felodipine (FD)–Eudragit® EPO (EPO) binary mixtures with pre-determined weight fractions were analysed using DSC to measure the endset of melting and glass transition temperature. Extrudates of 10 wt% FD–EPO were processed using temperatures (110°C, 126°C, 140°C and 150°C) selected from the temperature–composition (T–ϕ) phase diagrams and processing screw speed of 20, 100 and 200rpm. Extrudates were characterised using powder X-ray diffraction (PXRD), optical, polarised light and Raman microscopy. To ensure formation of a binary amorphous drug dispersion (ADD) at a specific composition, HME processing temperatures should at least be equal to, or exceed, the corresponding temperature value on the liquid–solid curve in a F–H T–ϕ phase diagram. If extruded between the spinodal and liquid–solid curve, the lack of thermodynamic forces to attain complete drug amorphisation may be compensated for through the use of an increased screw speed. Constructing F–H T–ϕ phase diagrams are valuable not only in the understanding drug–polymer miscibility behaviour but also in rationalising the selection of important processing parameters for HME to ensure miscibility of drug and polymer.

Shape stabilised phase change materials based on a high melt viscosity HDPE and paraffin waxes

Shape stabilised phase change materials (SSPCMs) based on a high density poly(ethylene)(hv-HDPE) with high (H-PW, Tm = 56–58 °C) and low (L-PW, Tm = 18–23 °C) melting point paraffin waxes were readily prepared using twin-screw extrusion. The thermo-physical properties of these materials were assessed using a combination of techniques and their suitability for latent heat thermal energy storage (LHTES) assessed. The melt processing temperature (160 °C) of the HDPE used was well below the onset of thermal decomposition of H-PW (220 °C), but above that for L-PW (130 °C), although the decomposition process extended over a range of 120 °C and the residence time of L-PW in the extruder was <30 s. The SSPCMs prepared had latent heats up to 89 J/g and the enthalpy values for H-PW in the respective blends decreased with increasing H-PW loading, as a consequence of co-crystallisation of H-PW and hv-HDPE. Static and dynamic mechanical analysis confirmed both waxes have a plasticisation effect on this HDPE. Irrespective of the mode of deformation (tension, flexural, compression) modulus and stress decreased with increased wax loading in the blend, but the H-PW blends were mechanically superior to those with L-PW.

Melt processing and properties of linear low density polyethylene-graphene nanoplatelet composites

Composites of Linear Low Density Polyethylene (LLDPE) and Graphene Nanoplatelets (GNPs) were processed using a twin screw extruder under different extrusion conditions. The effects of screw speed, feeder speed and GNP content on the electrical, thermal and mechanical properties of composites were investigated. The inclusion of GNPs in the matrix improved the thermal stability and conductivity by 2.7% and 43%, respectively. The electrical conductivity improved from 10−11 to 10−5 S/m at 150 rpm due to the high thermal stability of the GNPs and the formation of phonon and charge carrier networks in the polymer matrix. Higher extruder speeds result in a better distribution of the GNPs in the matrix and a significant increase in thermal stability and thermal conductivity. However, this effect is not significant for the electrical conductivity and tensile strength. The addition of GNPs increased the viscosity of the polymer, which will lead to higher processing power requirements. Increasing the extruder speed led to a reduction in viscosity, which is due to thermal degradation and/or chain scission. Thus, while high speeds result in better dispersions, the speed needs to be optimized to prevent detrimental impacts on the properties.

Optimization and Prediction of Mechanical and Thermal Properties of Graphene/LLDPE Nanocomposites by Using Artificial Neural Networks

The focus of this work is to develop the knowledge of prediction of the physical and chemical properties of processed linear low density polyethylene (LLDPE)/graphene nanoplatelets composites. Composites made from LLDPE reinforced with 1, 2, 4, 6, 8, and 10 wt% grade C graphene nanoplatelets (C-GNP) were processed in a twin screw extruder with three different screw speeds and feeder speeds (50, 100, and 150 rpm). These applied conditions are used to optimize the following properties: thermal conductivity, crystallization temperature, degradation temperature, and tensile strength while prediction of these properties was done through artificial neural network (ANN). The three first properties increased with increase in both screw speed and C-GNP content. The tensile strength reached a maximum value at 4 wt% C-GNP and a speed of 150 rpm as this represented the optimum condition for the stress transfer through the amorphous chains of the matrix to the C-GNP. ANN can be confidently used as a tool to predict the above material properties before investing in development programs and actual manufacturing, thus significantly saving money, time, and effort.